Polyvinyl resin plasticized with polyester



' amide, and triethanolamine hydrochloride. defect of these materials is that they are all per Patented Sept. 23, 1952 i uNiTEo STAT ES- PATENT OFFICETLV'.

POLYVINYL RESIN PLASTICIZED WITH POLYESTER Irving Piickel, Cambridga- Massa, assignor to Cambridge Industries Company, Cambridge,

Mass, a corporation of Massachusetts No Drawing.

Application January 16, 1950, Serial N0. 138,928

6 Claims. (01. QED-29.6)

, 1 This invention relates to resinous non-migrating plasticizers for polyvinyl acetate and polyvinyl alcohol compositions, and to the polyvinyl acetate and polyvinyl alcohol compositions plasticized therewith.

Because of their low cost, superior adhesive qualities and resistance to ultra-violet light, oxidation and ageing, polyvinyl acetate resins-suitably plasticized-have found wide usage as adhesives, and in coatings of all kinds. The available plasticizers which have been compatible with these polyvinyl acetate resins have been limited to the so-called chemical plasticizers, such as dibutyl phthalateand tricresyl phosphate. These plasticizers, because of their low molecular weight show some volatility at ordinary temperaturesandwill migrate out of films of the compound into such materials as paint and lacquer films, leather, paper, asphalt, etc.,

' with which they may be in contact. This limi--.

tation of plasticizers to the chemical type has precluded. the application of polyvinyl acetate resins to such usesas leather finishes, base coats for oil cloth, backing compounds for textiles and carpets, sealer coats for linoleum and asphaltimpregna'ted products, q binders for non-woven fabrics, etc.

Suitably plasticlzed polyvinyl alcohol resins have also found many industrial applications.

These applications are for the most part based on the resistance of polyvinyl alcohol to organic solvents, greases, fats, as halt, etc., the'rendering of polyvinyl alcohol films water-insoluble by treatment withcertainchromium compounds or with dimethylol urea, and the superior toughness of polyvinyl alcohol compositions as well as their high impermeability to most gases.

The -ester type, water-immiscible plasticizers commonly'used with plastics are, however, not

grades of polyvinyl'alcohol, and they are also of but little use with the p'artiallylhydrolyzed grades. None of the water-insolubleresinous type non-migrating plasticizers has been found compatible with the completely hydrolyzed 4 to becompatible with any of the polyvinyl alcoh'ol'ty peresins, even thosegrades which contain large proportions'or residual acetate groups. The products which hav'ebe'en found to be most effective in imparting softness, and flexibility to polyvinyl alcohol resins are some of the high boiling point, water-soluble organic compounds containing .hyd'roxylfamide and amino groups such as glycerine, ethylene glycol, ethanol acetmanently water-soluble and will leach out of polyvinyl alcohol compositions which contain them, even though the polyvinyl alcohol maybe insolubilized by treatment with chromium compounds or dimethylol urea. Since these compounds are all hygroscopic, a further defect inherent in their use is that the softness and flexibility of polyvinyl alcohol compositions containing them will vary greatly with the relative humidity of the surrounding atmosphere.

, A primary object of the present invention is the embodiment of resinous type plasticizers which are free of the aforementioned defects, 1. e., are compatible with an aqueous dispersion of polyvinyl acetate and with an aqueous dispersion of polyvinyl alcohol, especially partially hydrolyzed grades of polyvinyl alcohol, and will not migrate out ofthe films or other products made of the polyvinyl acetate or polyvinyl alcohol and plasticized therewith.

A further object of the invention is the embodiment of an aqueous dispersion of polyvinyl acetate compositions and an aqueous dispersion of polyvinyl alcohol compositions, especially of partially hydrolyzed grades of polyvinyl alcohol, having a'plasticizer according to the present invention incorporated therein and suitable for practical applications, such as the preparation of lasticized films, coatings, articles, etc;.

Further objects of the invention will be evident from the following examples setting forth pres ently preferred embodiments thereof, the said exam les being however entirely illustrative'and not at all limitativev in' character. 'In the said examples, parts by weight bear the same relation to parts by volume as does the kilogram to the liter. All tem eratures arein degreesFah'renheit. unless otherwise indicated. Briefly stated. the foregoing objects are-realized according to the present invention by the preparation and incorporation into a polyvinyl acetate composition and/or into a'composition of a partially hydrolyzed grade of polyvinyl alcohol of the products of the reaction-between adipic acid and diethylene glycol or dipro ylene glycol. These reaction products may advantageously-especiallywhen used for the plasticization of polyvinyl acetatebe fatty acid-modiiied and/or polyhydric alcohol-modified. To

. this end, use may be made of up to 4% by weight,

relative to the wei ht of-the reactionrproducts, of a vegetable oil fatty acid,- such assova bean oil fatty acids, and of up to 4% by weight. relative to the weight of the said reaction products, of an alcohol such as pentaervthritol. Other polyhydricalcohols such as glycerol. ethylene .glycol, hexaline glycol, triethylene glycol, tri- Example 1 557 parts by weight of adipic' acid and 443 parts by weight of diethylene glycol are placed, in a stainless steel varnish kettle having a capacity of about 2000 parts byvolume: The-mixture is heated to a temperature of 450overaperi0d. of 1 /2 hours and then maintained at this temperature for 2% hours. Oncooling; the paleviscous liquid has the following physical properties:

Per cent non-volatiles 100 Viscosity- (Gardner): Z1-Z2 Color (Gardner) 6 .Acid number 32 Yield parts :by weight ...848

-It may' beused as a plasticizer'for polyvinyl acetate resinous compositions as well as forpartiallyhydrolyzed polyvinyl alcohol compositions.

Example 2 1258 parts by weightof adipic acid, .Sdparts-by On-coohngl84l parts by weight .of a pale resinous mass are obtained having properties. similar to thoseof. theplasticizer. described inExample 1. 40 b'uthaving amuch .greater viscosity.

V Example} 1150 parts byweight-oi adipic acid, 366 parts v lziyxweight of?distilledsoya-beanoil fatty acids 4 and-"9B8parts'by weight ofrdiethylene' glycol'are placed. in av -necked 'fiaslr having a capacity of 3000 partsbyrvolume; and heatedin 1 /2 hours to attemperature-rofr 450 and maintained at this temperature for 2 hours; :partsaby weight of apale viscous-liquid are ob-- itained having properties similar to those offthe .plasticizer. described: in. Example; 1.

Example 4..

parts by weight ofjdistilled-soya bean oil fatty 1200partsby weight ofdipropylene glycol'and" 1200 parts by weight of adipicacid are placed in: a 3=neckedffiask having a capacity of 3000 parts bywolume, and-heated to a temperature of 450 overa period'of 1 /2 hours and maintained'at.

this temperature for 2 /2 hours. On cooling, :1900partsby weight'ofapale viscousliquid are obtained having properties similar to those of the. plasticizer: described in Example: 1';

. Example" 5 IZSBpa-rts'by-"Weight 'of-adipic acid, 200'parts On: cooling; 2089 50.

Example 6 1150 parts by weight of adipic acid, 366 parts by weight of distilled cottonseed oil fatty acids and 988 parts by weight of diethylene glycol are placed in a three-liter, threevnecked flask and heated in;1. hours:.to atemperature of 450 and maintained at this temperature for 2%; hours. On cooling, 2076 parts by weight of a pale viscous liquid are obtained having properties -similar-to;the:plasticizer described in Example 1.

Example 7 1l50'partsbyweight of adipic acid, 366 parts bygweightof distilled soya bean oil fatty acids and1250' parts by weight of dipropylene glycol are-placedyin a three-liter, three-necked flask and heated in 1 /2 hours to a temperature of 450 and maintained at this temperature for 2 hours. On cooling, 2339 parts by weight of a pale viscous liquid are obtained having properties similar to the' plasticizer 'describedfin Example 1.

'876 parts-by weight of 'adipicacid; 29'4- parts by weight of maleic anhydride and lnfio parts by weight of diethylene'glycol are placed'in'athreeliter, three necked flask and heated in 1%hours to a temperature of 233 C; and maintained at this temperature for"? hours. On cooling, 1820 0 partsby weight-of apale viscousliquidare' obtained having properties similar to the plasticizer described in Example -1 but having a much greater viscosity:

Emmp'led' 1000 ,partszby weight. of, succinic 'anhydride ,and .1160 parts. by. weight, of, diethylene. glyfi l, are heated in. a, three-liter, ,threerneckedg flash. in 1% hours.to.a..temperature 013 450.? .andmaintained at this. temperature foriz hours. On cooling, a pale. viscoushquid; having properties similar to theplasticizer described-in Example; 1

isobtained...

vExample.10.;

1000. parts; by+weightt of 1 .succinic;:anhydride and: 1470. parts 1: by: weight" of idipropylene: glycol are placed in a three-liter, three-necked flask, andheated in l nhours toatemperature of -.'450 and; maintained at. this::-temperature, for' 2 hours. Onxcooling; a.gpale;viscousrliquid having properties: similaritothez plastici-zer-described; in Example; 1 .isrobtainedi Example 11 .1258parts .byweig'ht .ofsuccinic =anhydride; 200

acids and 155.0. parts by weight of. diethylene glycol are placed,inathree-liter, three-necked fiaskandlheated in 1% hours to atemperature of 4509 andmaintained at .thistemperature for a DGIiOd-OfZ- /g hours. On cooling,- a, pale viscous liquid having properties similar to the plasticizer described in Example. .1. is-obtained.

Example '12- 1204 partsibyweightof adipicta'cid; 183' parts by weightof "soya' bean oil'fatty acids, 42'partsby weight of pure. pentaerythritoland 940 parts by weightjof diethylene glycol areplaced'in a threeliter; three-necked fiask'and heated to atemperature of 450over aiperiod of 1%,hoursand maintained at: this temperature. for a periodiof 2 hours; On'cooling,'.19.15parts by weight of a pale viscous liquid are. obtained having. properties similar "to; the. plasticizer; described Example 1.

1, to a'temperature of 450 and temperature for 2% hours.

tion of the resinous plasticizer. J vinyl alcohol compositions plasticized with these plasticizers show no tendency toward migration.

5 f Example 13' I 1258 parts by weight or adipicacid, 62'lparts by weight of glyc'erine and 900 parts by weight ofdiethyleneglycol were placed in a three-liter.

three-necked flask and heated to a temperature of 450 overa period of 1 /2 hours and maintained at thattemperature'for a period of 2 /2 hours.

, Oncooling, 1827 parts by weight of a pale viscous liquid was obtained having similar properties to the plasticizer' described in Example 1.

Example 14 g;

' 1258'parts by weight of adipic acid, 200 parts by weight of diglycolic acid and 1213 parts'by weight of diethylene glycol were placed in a threeliter, three-neckedflajsk and heated in 1% hours maintained at this parts by weight of a pale viscous liquid wasobtained having properties similar to the plasticizer described in Example 1.

The plasticizers described in Examples 1 to 14 i T are all compatible with polyvinyl acetate and with polyvinyl alcohol and when films are laid down from a solution of, for example, the plasticized polyvinyl acetate they are transparent,

I have good gloss and are rubbery in nature.

These films when overcoated with lacquer, drying oils, paints, varnishes, etc. show no migra- Similarly, poly- These resinous type plasticizers may easily be incorporated into polyvinyl acetate and polyvinyl alcohol compositions as shown by the following illustrative examples:

' Ezndmple 15 40 parts by weight of the plasticizer described in Example 1 are stirred into 100 parts by weight of an emulsion of polyvinyl acetate containing 54% polyvinyl acetate resin. Considerable thick- :ening ofthe emulsion takes place. This mixture is then thinned with 40 parts by weight of water to give a stable emulsion which yields films which are transparent and of a rubber-like nature.

Example 1 6 40 parts by weight of water are added slowly with stirring to 40 parts by weight of the plasticizer described inExample l. 100 parts by weight of a polyvinyl acetate emulsion containing 54% polyvinyl acetate resin are then added to the emulsion of plasticizer and water to produce a stable emulsion which yields films similar to those described in Example 15.

Example 1 7 3 parts by weight of 28% ammonia water are stirred into 40 parts by weight of the plasticizer described in Example 1 until a clear solution is obtained. 40 parts by weight of water are then added and stirred until a clear solution is obtained. 100 parts by weight of a polyvinyl "acetate emulsion containing 54% of polyvinyl acetate resin are added to the water solution of the plasticizer with stirring to produce a stable emulsion which yields films similar to those of Example 15.

Example 18 3 parts by weight of 28% ammonia water are On cooling,I 2 270 L tained. I 1100 parts by weight of a polyvinyiacetata emulsion containing 54 ofpolyvinyl acetate resinare added to the water solution of the plasticizer with stirring to producea stable emulsion which yields films similar to those of Example 15.

Example 19 18 parts by weight of lampblack, ,104 partsby weight of yellow iron oxide and 345 parts by weight of the plasticizer describedin Example 1 are mixed together to yield aviscous paste having an olive drab color. This paste is then ground on a three-roll paint mill-until. a smooth dispersion is obtained; 17 parts by weight of 28% ammonia water are then added with stirring to 367. parts by weight of the above paste and mixed until a homogeneous mass is. obtained. 175 parts by weight of water are then added and the .paste is stirred until the mixture is uniform. 470 parts by weight of a polyvinyl acetate emulsion con taining 54% of polyvinyl acetate resin are then added with stirring to yield a coating compound which is suitablefor impregnating cotton sheetin'g over which a coating of drying oil can 'beap- I plied. 1

'E'xample 20 v Cotton sheeting, of the type known as'airplane fabric, having a warp count. of .80 and a filling I ASA) The heat bodied oil is prepared byheating 180 count of 80 and weighing 3.7 ounces per square yard, is impregnated with the coating compound described in Example 19 and dried by festooning at 150 C. to remove the water- The sheeting increases in weight by 2.4 ounces per square yard and is substantially sealed. This. coated fabric is then coated evenly on each side, using a double doctor knife coating machine, with a pigmented coating composition consisting of thefollowing:

' Parts by weight Lampblack .47 Yellow iron oxide L "270 Heat bodied oil [1232 Cobalt naphthenate Soln. (6%. Co) 3.5 Lead naphthenate Soln. (24% Pb) 35.0 Antiskinning agent (National Aniline Divif parts by weight of China-wood oil in a stainless steel varnish kettle of a capacity of about :3000 parts by volume to a temperature of 500 in 1 hours. At this time, the kettle is removed from the fire, 36 parts by weight of 2-3 bodied (Gardner) linseed oil added, and the temperature al lowed to fall below 450. The heatbodie'd'oil is then thinned with 65 parts by weight of mineral spirits.

The coated fabric is now festooned in a steam room and cured at 150 for 10 hours. A total increase in weight of 1.4 ounces per square yard of this oil top coat is obtained, yielding a coated fabric having a weightof 7.5 ounces per square yard. This coated fabric has superior flexibility, drape and tear resistance relative to ordinary oilimpregnated cotton sheeting and because of the stirred into 40 parts by weight of the plasticizer described in Example 4 until a clearsolutionis obtained. 40 parts by weight of water are then added and stirred until a clear solution is obinertness of the polyvinyl acetate base boat has superior ageing characteristics.

' Example 21 7 parts by weight of 28% ammonia Water are added to parts by weight of the plasticizer described in Example 1. This mixture is stirred until a clear solution is obtained. The product is then added, with stirring, to 4000 parts by weight of a 5% solution of a 77% hydrolyzed polyvinyl acetate resin; 77% of the acetate .i:'i2,611,7,56 7 8 ig-gmqflgfihjtfdl'OlilZditOproyldeiiafi'fiblyyinylfllcized with a non-migratin viscous liquid resincbhol derivedfrom polyvinyl: acetate. .Films'cast Nous ,plastioizer said plasticizer consisting ..of the iromthe resultantvsolutiorr areclearandttransproduct of'reactionbetween amember selected jparent ;and=possess rubberelike: characteristics. from the group consisting-of adipic acid pand'suc- E'xampleez ljcinio anhydrideandamemherselectedfromthe group of diethylene. glycol and dipropylene; glycol, 7 Parts by Weight of ammonia Water are with up to 4% .of .anotherpolyhydric alcohol-and added to 100 parts by weightof the plasticiz r vwith up 130.14% of. avegetable oilfatty acid. describedinExamplefl. .This mixture is'stirred 1'2. A composition of matter comprising: essenuntil a clear solution 'isobtained. 1' The product; 10 tially an aqueousdispersion of polyvinyl acetate, *is then-added, as'in Example.21',"to 4000 partsby said dispersion being plasticized' with" a non- -weight-.of :a- 5% solution ofwa 77%...hydrolyzed migrating viscousliquidresinous plasticizer conpolyyinyl:-acetate resinyi. e.:.a polyvinyl :alcohol ....sisting. of .theproduct (ii-reactionbetweenadipic derived from. polyvinyl. acetate in which about [acid and diethylene glycol. I V-7% of thea ate ro p h ve been.hydrolyzed. l5 .3. ,A. composition of..matter..comprising .essenr .Ifilms cast ifrom the." resultant .zsolutionxare clear .,tial1y an. aqueous dispersioniof polyvinyl acetate, ".;e-anditransparentiandhave rubherelike character- .--said dispersion. beinggplasticized with. .a:non istics.

..migrating viscous liquid resinous plasticizer. con- Example: 23

imparts by Weightof. a 47%;hydrolyzed grade "Weightof the plasticizer described in Example 1 are dispersed in-an excess of hot methyl alcohol. After uniform dispersion is realized, the methyl zzzalcoholis. evaporated .ofi, leaving av clear rubbery amass. lThis rubbery mass is thenmilledon a hot trarubber .mill .to :removeoccluded methyl alcohol,

. .sistingpithe product. of. reactlon..-between.adipic acidand.dipropyleneglycbl.

4. A composition .oi.matter...comprising -essentiallyanaqueous.dispersion'oia partiallyhydro- .lyzed polyvinyl jacetate, .in .whichup. to 177% of .the polyvinyl acetate, groups .have..b.een hydrolyzed,.. said..disper sion plasticizedwith anon- ..migrating viscous liquid resinous...plasticizer. con- ...sistingof .the product ofreaction. between adipic .acidand.diethyleneglycoL.

. 5.. Acomposition .of -.matter comprising essen- ,30 tially. anaqueousdispersioniof.a. partially h dr .and is sheeted out. The product may. bemolded Y o :zonextrudedfor tubing, gaskets, etc., which have lyzedzp-olyv-myl acetate mwhichupm of-me L'ithBQBXOf-BllEllt solvent resistance of polyvinylsalgg g ay? "beennhydmlyzed' :;cohol'without;the :poor .moisture-sensitiyity; of 5 plasFmzed w damn epolyvinylzralcohol .pla-sticized JWith glycerine or. mg vlscouahquidlesmqus plasticizel-con 5 "other water-soluble plasticizer. The. composition g g gp i f .refictmn-between \adipic p a a py ne g yco fig gf s 91 pmecme fi m of ti A composition of matter comprising essena y an aqueous dispersion of polyvinyl acetate ..,Rroduc.ts..hav1ng essentially similar properties -'-.are obtained by replacing the Plasticizerused in il t l tplaspclzed P.-'- .iExam'p'les 1'5 to23 by the correspondingamount 25 3252 2? g f g gg g g i 2 7 c .0 .reac ion eweensuc- :giiy of theyother plasticizers precedingly .dis lcmmanhydnde anddiethylenefiglycoll As indicated hereinabove, .in the aqueous. dis- IRVING 63K131:-

persions of hydrolyzed polyvinyl acetate resins .up to "77% hydrolysis of polyvinyl acetate, and i-REEERENQEs BITE!) polyvinyl acetate, plasticized as set forth in Ex- The following references are ofrecord iii-"the '::.amples"-15.'23,' .the'plasticizer may be modified file of this patent:

-""with up to 4% of a polyhydric alcohol and up to I p '4 %:of a vegetable oilrfatty acid. The amount of UNITEDSTATES" BA'I'ENTS dded'polyhydric'alcohol and of added vegetable Number I Name v Date 13.011 .fattyacidmay be 0%, and up to 4% of the 4 Fuller pt ,'l94a8 ."alcohol'and may be 0% of vegetable oil fatty acid FQREIGN [EA-TENTS .i.-..and:upi'to..141% of thevegetable oil fatty acid. Number C t isFilmsprepared from the compositions prepared r 368 611 It mm W V V Date .iriaccordingfto the preceding examples may be 5 soaked, for instance in toluol, without any notice- 586826 i 1933 bl fi t reatBritam Apr 1, 7 .LHavingthusidisclosed the invention, what is F RENCES claimedisi .,De Bell. et'al.: German Plastics Pract' 1. A composition of matter comprising essen- 2273 5 223,. ubushed 9 6 pgiges stiallyan aqueous dispersion of a member selected ardson p 1 4 by De Ben and iromthe group consisting of partially hydrolyzed DuPont Technical D polyvi yl ac t in which up to of t p y- .ceived in Patent Omce i rgtgfiti fi ie igfiggifi' ayinylacetategroups have been hydrolyzed and g;'.-polyyinyla:acetate,r said. dispersion being plasti- 

1. A COMPOSITION OF MATTER COMPRISING ESSENTIALLY AN AQUEOUS DISPERSION OF A MEMBER SELECTED FROM THE GROUP CONSISTING OF PARTIALLY HYDROLYZED POLYVINYL ACETATE IN WHICH UP TO 77% OF THE POLYVINYL ACETATE GROUPS HAVE BEEN HYDROLYZED AND POLYVINYL ACETATE, SAID DISPERSION BEING PLASTICIZED WITH A NON-MIGRATING, VISCOUS LIQUID RESINOUS PLASTICIZER, SAID PLASTICIZER CONSISTING OF THE PRODUCT OF REACTION BETWEEN A MEMBER SELECTED FROM THE GROUP CONSISTING OF ADIPIC ACID AND SUCCINIC ANHYDRIDE AND A MEMBER SELECTED FROM THE GROUP OF DIETHYLENE GLYCOL AND DIPROPYLENE GLYCOL, WITH UP TO 4% OF ANOTHER POLYHYDRIC ALCOHOL AND WITH UP TO 14% OF A VEGETABLE OIL FATTY ACID. 